Water soluble sulphonated



Patented May 19, 1936 STATES WATER SOLUBLE SULPHONA'IED GONDENSATION PRODUCTS Ernst Alfred Mauersberger, Maarssen, near Utrecht, Netherlands No Drawing. Application March 14, 1935, Serial No. 11,046. In Germany September 20, 1934 6 Claims. (Cl. 260-9912) My invention relates to certain new watersoluble preparations made from woolfat alcohols and particularly from the cholesterin bodies thereof and their derivatives, and to the process of producing such preparations.

woolfat alcohols and the cholesterin bodies preponderatingly present therein are cheap and very readily accessible, but they have heretofore not been used practically because the reaction 10 products of these bodies were found to be highly unstable. Attempts were made to use such reaction products in the textile industry, but because of the instability of the products these attempts resulted in failure.

The cholesterin bodies which make up the bulk of woolfat alcohols of variousorigins are isocholesterin, oxycholesterin, metacholesterin, cholesterin and others, and while these bodies are partly emulsified with water, nevertheless the emulsions are very tough and quickly give off their water, leaving a hard, tough, porous body which practically contains no water.

By sulphonating the cholesterin bodies under very careful operating conditions in a strongly acid medium, soluble products were obtained which, however, decompose as soon as diluted with water, so that the product really obtained was a solution of the cholesterin body in the sulphonating medium. If a powerful sulphonating medium, such as chlorsulphonic acid, be used,

only pure black, tar-like, insoluble decomposition products are obtained. These results are due primarily to the hydroxyl group which is secondarily attached in the cholesterin bodies.

Mixed sulphonation of woolfat alcohols or of the cholesterin bodies produced therefrom, with such well-known fatty alcohols as lauric alcohol, cetyl alcohol or oleic alcohol and the like gave no satisfactory results as only about 15% of the cholesterin bodies could be used if soluble products were to be obtained at all. Upon using more than 15% of the cholesterin bodies, the latter separated out in the aqueous solution of the sulphonate and, as a matter of fact, in this 5 sulphonating procedure the woolfat alcohol and its cholesterin bodies did not enter into the reaction but were merely carried along as ballast bodies which were emulsified by the fatty alcohol sulphonate which formed.

The principal object of my invention is to produce new clearly water soluble highly useful condensation products from woolfat alcohols and particularly from the cholesterin bodies thereof and their derivatives, and I accomplish this object by first esterifying the cholesterin bodies (which are secondary alcohols) with boric acid and subjecting the cholesterin borlc acid esters or borate to treatment with a sulphonating medium in the presence of a boric acid ester or borate of an aliphatic alcohol. In this procedure it is desirable to use molecular equivalent quantities oi cholesterin borate and fatty alcohol borate.

It may be pointed out that for the purpose 01 my invention it is not necessary to first separate the cholesterin bodies out of the woolfat alcohol: if the latter consist preponderatingly of cholesterin. In this case the woolfat alcohols may bi used directly as such after previous esterification with borlc acid.

In carrying out my process two parallel reactions occur. The aliphatic chain of the fatt: alcohol borate is condensed with asatisfactor: yield at the cholesterin bodies, the condensatioi probably occurring in the cyclic body of th cholesterin molecule. At the same time sulpho nation of the enlarged cholesterin molecule take place. Very little can as yet be said with cer tainty regarding the course of the reaction, bu in any event all the cholesterin bodies undoubt edly participate in the reaction.

The resulting acid reaction products may b neutralized in the manner well known in this 9.! by any of the alkaline reacting agents, such a caustic soda or potash solution, ammonia as ga or in solution, amides, pyridine, etc.

The new substances obtained in accordanc with my invention dissolve very easily and clear] in water with a weakly yellow color. When i dehydrated condition they appear as a ligh hygroscopic light yellow powder which can i: very easily bailed together. By treating the past with about 1% of a 30% hydrogen peroxide solt tion, and permitting the entire mass to stand f two days, the color tone may be material bleached.

For the purpose of producing the new sul stance I may start with the cholesterin bodies woolfat alcohols, such bodies being previousi freed of aliphatic constituents and the alcoho being separated by fractionation. I may als alternatively, start with the whole alcohol of ti woolfat, particularly if the alcohol consists pri ponderatingly of cholesterin bodies. These a cohols are first esterified with boric acid. Tl borates of the fatty alcohols which cooperate the condensing action are produced from satl rated or unsaturated aliphatic primary alcohoi The sulphonating and condensing medium r quired for the reaction may consist of. about a sulphuric acid or of higher concentration or m an have anhydride added thereto. The reacn temperature may vary between 20 to 70 C., pendent on the strength of the sulphonating :dium. To obtain final products as light in .or as possible, it is desirable not to exceed a nperature of about 50 C.

The final products of my invention are excellt wetting, washing, emulsifying and, more )ecially, softening media, which are applicable the textile, leather and cosmetic industries, in a household, for improvement of high grade LPS and the like. By reason of their prounced softening action they may be used to prove the alkylated aromatic sulphonic acids, .smuch as they favorably aifect the latter, and air emulsions with fats, oils, waxes and the a are usuable for clearing or brightening purlBS.

the following examples will serve to illustrate invention.

Example 1 Vooli'at alcohols obtained by saponifying and billing the extraction of Breadford woolfat, are |jected to fractional distillation of high vacuand the fraction distilling over about 230 C. a vacuum of 3 mm. is caught up. This frac- 1 contains the cholesterin bodies and amounts 50 to 60% of the entire alcohol. 50 parts of s cholesterin fraction are esterifled in vacuo.

h 4 parts of commercial boric acid, the ester reupon cooled to 60 C. and mixed and thor- :hly stirred with 40 parts of orthoboric acid :r of oleic alcohol. The mixture is cooled down 20 C. resulting in the production of a viscid, ,ow, clear oil. While stirring and cooling, 50 ts of a 95% sulphuric acid are slowly intro- :ed into the oil, the temperature being mainred at about 35 C. As soon as all the sullric acid has been introduced, a stirring is conied for about an hour and the mixture is led down to 25 C. The acid sulphonation l condensation product is now introduced into parts of cold water, further cooling being ef- ;ed. The product dissolves in the water very :kly. Thereupon the diluted product is neuized with a 40% caustic soda solution at tematures between 20 and 25 C. The final prodis a light yellow paste which may be sprayed an appropriate apparatus to form a light yellightweight, hygroscopic powder which can easily balled together.

Example 2 'erman woolfat yields woolfat alcohols which sist of about 70% of cholesterin bodies and of aliphatic high molecular, saturated and aturated wax alcohols. These woolfat alcoare esterified in vacuo with about 8% of comcial boric acid and 50 parts of the resulting acid ester are mixed with 40 parts of cetyl rte. The mixture is cooled to about 30 C., at a temperature not exceeding 35 C. 45 :s of commercial sulphuric acid are stirred into the mixture. Thorough stirring of the entire mixture is continued for about one hour and one-half and this acid product is then introduced into 90 parts of water at a temperature not in excess of 25 C. Neutralization is then effected with a 40% caustic soda solution at a temperature between 20 and 25 C. and the product may be converted into powder form, as in Example 1.

Example 3 spraying, and by treating the paste with about 1 of a 30% hydrogen peroxide solution the color tone may be materially improved.

I claim:

1. As a new composition of matter, the sulphuric acid ester of the condensation product of a boric acid ester of an aliphatic alcohol with a boricacid ester of a cholesterin body, said aliphatic alcohol containing at least ten carbon atoms in the molecule.

2. The herein described process of producing sulphonated condensation products which process comprises forming a boric acid ester of a substance selected from the class of woolfat alcohols consisting mainly of cholesterol bodies, condensing said esters in the presence of a sulphonating agent with a boric acid ester of an aliphatic alcohol containing at least ten carbon atoms in the molecule and neutralizing the resulting products.

3. The hereindescribed process of producing sulphonated condensation bodies, which process comprises forming a boric acid'ester of cholesterin bodies of woolfat alcohols, condensing said esters in the presence of a sulphonating agent with a boric acid ester of an aliphatic alcohol containing at least ten carbon atoms in the molecule and neutralizing said products.

4. The herein described process of producing sulphonated condensation products, which process comprises the steps of claim 2 andthe additional step of bleaching the neutralized product.

5. As a new composition of matter, the neutralized reaction product of condensing a boric acid ester of. a woolfat alcohol with the boric acid ester of oleic alcohol in the presence of a sulphonating agent.

6. As a new composition of matter, the neutralized reaction product of condensing a boric acid ester of a cholesterol body of woolfat alcohols with the boric acid ester of cetyl alcohol in the presence of a sulphonating agent.

ERNST ALFRED MAUERSBERGER. 

